Binder resin compositions, production process and use thereof

ABSTRACT

The invention provides a novel binder resin composition with good adherence onto prime materials of polyolefin, poly (vinyl chloride), polycarbonate, PET, ABS and nylon, and also with excellent solvent solubility. A binder resin composition characterized by being chlorinated propylenic random copolymer with weight average molecular weight of 3000 to 250000, wherein propylenic random copolymer with melting point (Tm) measured by differential scanning calorimeter (DSC) of 115 to 165° C. obtained by copolymerizing propylene with other α-olefin in the coexistence of metallocene type catalyst is chlorinated to chlorine content of 10 to 40% by weight, after thermal degradation or directly without thermal degradation, and/or a binder resin composition characterized by containing carboxyl group-containing chlorinated propylenic random copolymer with weight average molecular weight of 30000 to 220000, wherein propylenic random copolymer with melting point (Tm) measured by differential scanning calorimeter (DSC) of 115 to 165° C. obtained by copolymerizing propylene with other α-olefin in the coexistence of metallocene type catalyst is grafted with α,β-unsaturated carboxylic acid or its anhydride in amounts of 0.1 to 20% by weight, after thermal degradation or directly without thermal degradation, and then chlorinated to chlorine content of 10 to 40% by weight, stabilizer and organic solvent.

TECHNICAL FIELD

The present invention relates to a binder resin composition to be usedfor the purpose of protection or beautiful ornament of polyolefinicresins such as polypropylene, polyethylene, ethylene-propylene copolymerand ethylene-propylene-diene copolymer, vinyl chloride resin,polycarbonate (PC) resin, poly(ethylene terephthalate) (PET) resin,acrylonitrile-butadiene-styrene (ABS) resin and nylon resin, and methodfor the production thereof. In more detail, it relates to a binder resincomposition for paint, printing ink, adhesive or primer that exhibitsexcellent adherence and other physical properties to sheets, films andmoldings of these polyolefin, poly(vinyl chloride), polycarbonate, PET,ABS and nylon.

BACKGROUND TECHNOLOGIES

Because of many advantages of light weight, antirust, broad degree offreedom for design, etc., in recent years, plastics are used extensivelyas materials for automotive parts, electrical parts, building materials,etc. Above all, because of low price and many excellent properties suchas moldability, chemical resistance, heat resistance, water resistance,good electrical characteristics, polyolefinic resins are used in a widerange as industrial materials and the growth of demand is also expectedin future. Different from synthetic resins with polarity, however,polyolefinic resin is nonpolar and crystalline, hence it has also adrawback of difficult adhesion with it.

For this reason, as a pretreatment for painting and adhesion, method ofproviding plasma treatment or gas flame treatment onto the surface ofmoldings to activate, or method of painting primer (undercoating agent)having chlorinated polyolefin as a major component is adopted.

For the painting of polypropylene bumper of automobiles, for example,primer compositions having chlorinated modified polyolefin as a majorcomponent are disclosed in Japanese Unexamined Patent Publication No.Sho 57-36128 and Japanese Patent Publication No. Sho 63-36624.

With these primers comprising chlorinated products, the adherence ontopolyolefin having been produced hitherto is excellent, but, it is thepresent situation that, with the advent of high-modularization of primematerial and low-temperature baking in recent years, prime materialsthat give insufficient adherence are seen, making it impossible tocorrespond sufficiently with conventional chlorinated polyolefinicresins.

Furthermore, it is the present situation that the chlorinatedpolyolefinic resins exhibit relatively excellent adherence ontopolypropylene prime material, but the adherence is insufficient ontoother prime materials (poly(vinyl chloride), polycarbonate, PET, ABS andnylon).

The chlorinated polyolefin resins etc. having been proposed hithertowere those having chlorinated isotactic polypropylene (hereinafter IPP),wherein IPP produced by using Ziegler-Natta catalyst as a polymerizationcatalyst was chlorinated, as a major component.

Whereas, an adhesive that uses chlorinated syndiotactic polypropylene(hereinafter SPP), wherein SPP produced by using metallocene compound asa polymerization catalyst was chlorinated is disclosed (Japanese PatentNo. 3045498 and Japanese Unexamined Patent Publication No. Hei 7-18016).However, this chlorinated SPP has more improved solvent solubility thanthat of conventional chlorinated IPP produced by using Ziegler-Nattacatalyst as a polymerization catalyst, but it exhibited excellentadherence only when the prime material is polypropylene and it has adrawback of insufficient adherence onto other prime materials(poly(vinyl chloride), polycarbonate, PET, ABS and nylon).

The purpose of the invention is to provide a binder resin compositionwith good adherence and gasohol resistance to various polyolefinsincluding polypropylene prime material, poly(vinyl chloride),polycarbonate, PET, ABS and nylon prime materials and also withexcellent solvent solubility.

DISCLOSURE OF THE INVENTION

The inventors have come to solve the problems aforementioned with abinder resin composition characterized by being chlorinated propylenicrandom copolymer with weight average molecular weight of 3000 to 250000,wherein propylenic random copolymer with melting point (Tm) measured bydifferential scanning calorimeter (DSC) of 115 to 165° C. obtained bycopolymerizing propylene with other α-olefin in the coexistence ofmetallocene type catalyst was chlorinated to chlorine content of 10 to40% by weight, after thermal degradation or directly without thermaldegradation, and/or a binder resin composition characterized by beingcarboxyl group-containing chlorinated propylenic random copolymer withweight average molecular weight of 30000 to 220000, wherein propylenicrandom copolymer with melting point (Tm) measured by differentialscanning calorimeter (DSC) of 115 to 165° C. obtained by copolymerizingpropylene with other α-olefin in the coexistence of metallocene typecatalyst was grafted with α,β-unsaturated carboxylic acid or itsanhydride, after thermal degradation or directly without thermaldegradation, and then chlorinated to chlorine content of 10 to 40% byweight.

The propylenic random copolymer being raw material of the invention is acopolymer obtained by copolymerizing propylene being major componentwith other α-olefin using metallocene catalyst as a polymerizationcatalyst. Commercial products such as Wintech (from Nippon Polychem Co.,Ltd.) can also be used.

For the other α-olefin being comonomer, at least one kind can beselected from ethylene or a group consisting of olefins with number ofcarbon atoms of 4 or more. As the olefins with number of carbon atoms of4 or more, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. can bementioned. By using metallocene catalyst, the range of copolymerizablecomonomers can be widened over Ziegler-Natta catalyst.

For the metallocene catalyst to be used in the invention, publicly knownone can be used. Concretely, such catalyst obtainable by combiningcomponents (A) and (B), and, if need be, additionally (C) describedbelow is preferable.

Component (A): Metallocene complex being a compound of transition metalthat belongs to groups 4 to 6 in the periodic table having at least oneof conjugate 5-membered ring ligand.

Component (B): Cocatalyst capable of activating said metallocene complex(A) by reacting compound (B) with metallocene complex (A)(ion-exchangeable stratified silicate).

Component (C): Organic aluminum compound.

The propylenic random copolymer of the invention can be produced bypublicly known methods (Japanese Unexamined Patent Publication No.2001-206914 etc.). For example, while supplying propylene, ethylene andhydrogen into the reactor and while continuously adding alkyl aluminumand metallocene catalyst, the production is performed.

The propylenic random copolymer of the invention is preferable to havemelting point (hereinafter Tm) measured by differential scanningcalorimeter (hereinafter DSC) of 115 to 165° C. If higher than 165° C.,then the solvent solubility decreases. If lower than 115° C., then theadherence onto prime materials decreases. More preferable is low-meltingpoint propylenic random copolymer with 115 to 135° C. Besides, in themeasuring method of Tm by DSC in the invention, the evaluation was madewith both peak temperature of melting and end temperature of melting atthe time when sample (ca. 5 mg) was taken and molten for 5 minutes at200° C., and, after lowering the temperature to 40° C. at a rate of 10°C./min to crystallize, the temperature was raised further to 200° C. ata rate of 10° C./min to melt, using DSC measurement apparatus from SeikoCo.

For the propylenic random copolymer of the invention, it doesn't matterwhether one thermally degraded at a temperature above melting point andbelow 350° C. in the presence of radical generator or one withoutthermal degradation is used solely or by mixing, employing Banburymixer, kneader, extruder or the like. The radical generator to be usedfor the reaction can be selected appropriately from publicly known ones,but, in particular, organic peroxide type compound is desirable.

As said organic peroxide type compounds, for example, di-t-butylperoxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide,dilauryl peroxide, cumene hydroperoxide, t-butyl hydroperoxide,1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, cyclohexanone peroxide, t-butylperoxybenzoate, t-butylperoxy isobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethyl hexanoate, t-butylperoxyisopropylcarbonate, cumylperoxy octoate, etc. are mentioned.

The chlorinated propylenic random copolymer of the invention can beobtained by introducing chlorine to said propylenic random copolymer.The chlorination reaction is conducted by dissolving said propylenicrandom copolymer into chlorine-based solvent such as chloroform, andthen by blowing-in gaseous chlorine while irradiating ultraviolet raysor in the presence of said organic peroxide.

The chlorine content is optimum to be 10 to 40% by weight, preferably 15to 30% by weight. If lower than this range, then the adherence ontovarious prime materials becomes better, but the solubility into organicsolvent decreases. Also, If higher than this range, then the adherenceonto various prime materials decreases. Besides, the chlorine content isa value measured according to JIS-K7229.

The weight average molecular weight (hereinafter Mw) of the chlorinatedpropylenic random copolymer to be used in the invention is 3000 to250000. If under 3000, the cohesion of resin is insufficient, and, ifover 250000, then the handlings of ink and adhesive are lowered, whichis unpreferable. Besides, the Mw in the invention is a value measured bymeans of gel permeation chromatography (hereinafter GPC, standardsubstance: polystyrene resin).

Moreover, the carboxyl group-containing chlorinated propylenic randomcopolymer of the invention can be obtained by introducingα,β-unsaturated carboxylic acid and chlorine to said propylenic randomcopolymer and the production thereof is possible by two methodsmentioned below; namely, a method (first method) wherein, after directlygraft polymerizing α,β-unsaturated carboxylic acid or its anhydride ontothermally degraded propylenic random copolymer or propylenic randomcopolymer without thermal degradation, the chlorination reaction isconducted, and a method (second method) wherein, after the chlorinationreaction, α,β-unsaturated carboxylic acid or its anhydride is graftpolymerized.

In following, concrete methods for the production will be exemplified.In the first method, first the method of directly graft copolymerizatingα,β-unsaturated carboxylic acid or its anhydride onto thermally degradedpropylenic random copolymer or propylenic random copolymer withoutthermal degradation can be performed by publicly known methods of amethod (melt method) wherein said rein is molten by heating abovemelting point in the presence of radical generator to react, a method(solution method) wherein said rein is dissolved into organic solventand then the solution is stirred under heating in the presence ofradical generator to react, and the like.

In the case of the melt method, the reaction is conducted for a shorttime at a temperature above melting point and below 350° C. employingBanbury mixer, kneader, extruder or the like, hence it has an advantageof simple manipulation.

On the other hand, in the case of the solution method, aromatic solventsuch as toluene or xylene is used desirably as an organic solvent, but,besides, it may also be safe to use ester solvent, ketonic solvent orthe like by mixing partially. The radical generator to be used for thereaction can be selected appropriately from publicly known ones, but, inparticular, organic peroxide type compound is desirable and compoundslisted above can be used.

However, in the case of the second method, when conducting thechlorination reaction after α,β-unsaturated carboxylic acid or itsanhydride was graft copolymerized, it is required to replace saidsolvent with chlorinating solvent such as chloroform, hence, in thefirst method, melt method is more preferable.

Said chlorination reaction to be conducted after carboxyl groupmodification is performed by dissolving propylenic random copolymer orpropylenic random copolymer graft copolymerized with α,β-unsaturatedcarboxylic acid or its anhydride into chlorine-based solvent such aschloroform and then by blowing-in gaseous chlorine while irradiatingultraviolet rays or in the presence of said organic peroxide.

In the method wherein, after the chlorination reaction, α,β-unsaturatedcarboxylic acid or its anhydride is graft polymerized being the secondmethod, first, propylenic random copolymer is dissolved intochlorine-based solvent such as chloroform and the chlorination reactionis conducted similarly to the first method to produce chlorinatedpropylenic random copolymer, then solvent is changed to a solvent suchas toluene or xylene, and α, β-unsaturated carboxylic acid or itsanhydride is graft copolymerized in the presence of said organicperoxide. The reaction can be carried out at a temperature above 50° C.and below the boiling point of solvent. However, in the second method,the graft polymerizability of α,β-unsaturated carboxylic acid or itsanhydride is low at the reaction temperature above 50° C. and below 100°C., and the chlorinated propylenic random copolymer has a potential tocause the de-hydrochloric acid above 100° C. and below the boiling pointof solvent. Hence the first method is more preferable than the secondmethod.

The purpose of graft copolymerizing α,β-unsaturated carboxylic acid orits anhydride onto propylenic random copolymer in the first method is toafford the adherence to upper coating paint when using the binder resincomposition of the invention as a primer. The chlorinated polyolefin hasoriginally low polarity, hence, when using as a primer (undercoatingagent) as it is, the adherence onto PP prime material is good, butlittle adherence is seen onto high-polar upper coating paints (e.g.polyurethane paint and melamine paint). Hence it becomes important toenhance the polarity of chlorinated polyolefin by graft copolymerizingα,β-unsaturated carboxylic acid or its anhydride. As usableα,β-unsaturated carboxylic acids or their anhydrides, for example,maleic acid, citraconic acid, itaconic acid, aconitic acid and theiranhydrides, acrylic acid, methacrylic acid, fumaric acid, mesaconicacid, etc. are exemplified, but, when considering the grafting abilityonto polyolefin resin, maleic anhydride is most suitable.

In the invention, the amount to be introduced by graft copolymerizingα,β-unsaturated carboxylic acid or its anhydride is optimum to be 0 to20% by weight and preferable is 0 to 10% by weight. If over 10% byweight, the moisture resistance tends to decrease when using as aprimer.

The chlorine content is optimum to be 10 to 40% by weight, preferably 15to 30% by weight. If lower than this range, then the adherence ontovarious prime materials becomes better, but the solubility into organicsolvent decreases. Also, If higher than this range, then the adherenceonto various prime materials decreases. Besides, the chlorine content isa value measured according to JIS-K7229.

The weight average molecular weight (hereinafter Mw) of the chlorinatedpropylenic random copolymer and the carboxyl group-containingchlorinated propylenic random copolymer to be used in the invention is3000 to 250000 in the former. If under 3000, the cohesion of resin isinsufficient, and, if over 250000, then the spraying property decreases,which is unpreferable. Also in the case of the latter, it is 30000 to220000. If under 30000, the cohesion of resin is insufficient, and, ifover 220000, then the spraying property decreases, which isunpreferable. Besides, the Mw in the invention is a value measured bymeans of gel permeation chromatography (hereinafter GPC, standardsubstance: polystyrene resin).

The chlorinated polyolefin accompanies the de-hydrochloric acid todegrade when exposing to ultraviolet rays or high temperature. When thechlorinated polyolefin causes the degradation by de-hydrochloric acid,decreased physical properties such as decreased adherence ontopolypropylene prime material as well as coloring of resin, andaggravation of working environment due to freed hydrochloric acid arecaused. From these facts, it is required to add a stabilizer. Forobtaining this effect, it is preferable to add 0.1 to 5% by weight ofstabilizer based on the resin component (solids). As the stabilizer,epoxy compound can be exemplified. The epoxy compound is notparticularly restricted, but one compatible with chlorinated resin ispreferable and such epoxy compound with epoxy equivalent of around 100to 500 and with one or more epoxy groups in a molecule can beexemplified. For example, epoxidated soybean oil and epoxidated linseedoil epoxidated natural vegetable oils with unsaturated group withperacid such as peracetic acid, epoxidated fatty acid esters epoxidatedunsaturated fatty acids such as oleic acid, tall oil fatty acid andsoybean oil fatty acid, epoxidated alicyclic compounds represented byepoxidated tetrahydrophthalate, condensation products of bisphenol A andpolyhydric alcohols with epichlorohydrin, for example, bisphenol Aglycidyl ether, ethylene glycol glycidyl ether, propylene glycolglycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidylether, etc. can be exemplified. Moreover, monoepoxy compoundsrepresented by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decylglycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenylglycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenylglycidyl ether, phenol polyethylene oxide glycidyl ether, etc. areexemplified. Moreover, metallic soaps such as calcium stearate and leadstearate used as stabilizers for poly(vinyl chloride) resin,organometallic compounds such as dibutyl tin dilaurate and dibutylmaleate and hydrotalcite compounds can also be used, and it may be safeto use these in combination.

The composition of the invention can also be used after dissolved intoorganic solvent. The solution concentration may be selectedappropriately depending on the uses, but, the coating workability isinjured at either too high or too low solution concentration, hence theresin concentration is preferable to be 5 to 60% by weight. For thesolvent to be used, aromatic solvents such as toluene and xylene arepreferable, and, besides, ester solvents such as ethyl acetate and butylacetate, ketonic solvents such as methyl ethyl ketone and methylisobutyl ketone, aliphatic solvents such as n-hexane and heptane,alicyclic solvents such as cyclohexane, methylcyclohexane andethylcyclohexane can be used. In addition, for enhancing thepreservative stability of resin solution, it is preferable to addalcohols such as methanol, ethanol and isopropyl alcohol, propylenicglycol ethers such as propylene glycol methyl ether, propylene glycolethyl ether and propylene glycol tertiary-butyl ether solely or bymixing two or more kinds in amounts of 1 to 20% by weight based on saidsolvent. The recipe when dissolving the binder resin composition of theinvention into organic solvent is possible by converting thechlorinating solvent such as chloroform being reaction solvent to saidsolvent using the difference of boiling point. Also, it may be safethat, after epoxy compound etc. were added to the reaction liquor havingfinished the reaction as stabilizers, it is fed to a vent extruderequipped with solvent-removing suction portion at screw shaft section tosolidify and then dissolved into said solvent. The solidification can becarried out by the methods already known publicly, for example, by usingvent extruder equipped with underwater cutting pelletizer at blow-offopening portion of extruder, vent extruder and pelletizer that cutsstrand-like resin, etc.

The binder resin composition according to the invention can be used as apaint, printing ink, adhesive and primer applicable to films, sheets andmoldings of polyolefin, poly(vinyl chloride), polycarbonate, PET, ABSand nylon. It may be used by coating as it is, but solvent, pigment andother additives may be added within a range not injuring the effect ofthe invention. Moreover, although said composition exhibits balancedphysical properties of coated film by itself, it may be safe to use byfurther adding cyclized rubber, petroleum resin, cumarone-indene resin,chlorinated polyolefin resin, acrylic resin, alkyd resin, etc., if needbe. In particular, it is preferable to contain the binder resincomposition of the invention in amounts of 30% or more by weight.

EMBODIMENT TO PUT THE INVENTION INTO PRACTICE

One of the features of the propylenic random copolymer produced by usingmetallocene catalyst as a polymerization catalyst is that it has a lowermelting point-glass transition point than that of the propylenic randomcopolymer produced by using conventional Ziegler•Natta catalyst as apolymerization catalyst. It is considered therefore that, even if makingthe chlorine content low, the solvent solubility is good, andadditionally, due to lower melting point, the adherence at the time oflow-temperature baking becomes good.

Moreover, it is mentioned that, as a feature of the propylenic randomcopolymer produced by using metallocene catalyst as a polymerizationcatalyst, the molecular weight distribution is very narrow (Mw/Mn=ca. 2or less).

Furthermore, it has also newly become clear that, in the case of thepropylenic random copolymer produced by using conventional Ziegler•Nattacatalyst as a polymerization catalyst, decrease in the molecular weight,that is, formation of low-molecular weight components is causedinevitably, but, in the case of the propylenic random copolymer producedby using metallocene catalyst as a polymerization catalyst, formationthereof is little, because organic peroxide etc. are used when graftcopolymerizing α,β-unsaturated carboxylic acid or its anhydride.

In the invention, although no distinct reason is seen, it has been foundthat, different from the propylenic random copolymer produced by usingconventional Ziegler-Natta catalyst as a polymerization catalyst, thepropylenic random copolymer produced by using metallocene catalyst as apolymerization catalyst exhibits excellent adherence onto wide range ofprime materials such as poly(vinyl chloride), polycarbonate, PET, ABSand nylon, besides polyolefinic prime materials. Moreover, it isconsidered that, by using the propylenic random copolymer with lesslow-molecular weight components, produced by using metallocene catalystas a polymerization catalyst, the gasohol resistance became good.

In following, the invention will be illustrated concretely based onexamples, but the invention is not confined thereto.

EXAMPLE-1

A propylenic random copolymer (propylene ca. 97%-ethylene ca. 3%) (fromNippon Polychem Co., Ltd., MFR=2.0 g/10 min, Tm=125° C.) produced byusing metallocene catalyst as a polymerization catalyst was fed into adouble shaft extruder set at a barrel temperature of 350° C. to degradethermally, thus obtaining a propylenic random copolymer with meltviscosity at 190° C. of about 1500 mPa·s. In a glass-lined reactor wereput 500 g of this resin. After 5 L of chloroform were added, gaseouschlorine was blown-in from the bottom of reactor under a pressure of 2kg/cm², while irradiating ultraviolet rays to chlorinate. On the way,3-point samplings were made and chloroform being solvent was distilledoff by evaporator. Thereafter, replacement was made withtoluene/cyclohexane=70/30 (weight ratio) and Epicote 828 (fromYuka-Shell Epoxy Co., Ltd.) was added in amounts of 2% by weight basedon resin as a stabilizer to obtain resin solutions of chlorinatedpropylenic random copolymer with resin concentration of 20% by weight.The physical properties of the resins are shown in Table 1. The resinsolutions obtained were allowed to stand for one month at roomtemperature, but no changes were seen in the liquid state andappearance.

EXAMPLE-2

In a glass-lined reactor were put 500 g of propylenic random copolymer(propylene ca. 97%-ethylene ca. 3%) (Wintech, from Nippon Polychem Co.,Ltd., MFR=2.0 g/10 min, Tm=125° C.) produced by using metallocenecatalyst as a polymerization catalyst. After 5 L of chloroform wereadded, gaseous chlorine was blown-in from the bottom of reactor under apressure of 2 kg/cm², while irradiating ultraviolet rays to chlorinate.On the way, 3-point samplings were made and chloroform being solvent wasdistilled off by evaporator. Thereafter, replacement was made withtoluene/cyclohexane=70/30 (weight ratio) and Epiol TB (from Nippon Oiland Fats Co., Ltd.) was added in amounts of 2% by weight based on resinas a stabilizer to obtain resin solutions of chlorinated propylenicrandom copolymer with resin concentration of 20% by weight. The physicalproperties of the resins are shown in Table 1. The resin solutionsobtained were allowed to stand for one month at room temperature, but nochanges were seen in the liquid state and appearance.

EXAMPLE-3

A propylenic random copolymer (propylene ca. 97%-ethylene ca. 3%) (fromNippon Polychem Co., Ltd., MFR=2.0 g/10 min, Tm=125° C.) produced byusing metallocene catalyst as a polymerization catalyst was fed into adouble shaft extruder set at a barrel temperature of 350° C. to degradethermally, thus obtaining a propylenic random copolymer with meltviscosity at 190° C. of about 2000 mPa·s. In a four-neck flask attachedwith stirrer, condenser, thermometer and dropping funnel, 500 g of thisresin was molten by heating at 190° C. After nitrogen replacement inflask was performed for 10 minutes, 25 g of maleic anhydride were put-inover about 5 minutes while stirring, and 2 g of di-t-butyl peroxide wereadded dropwise over about 30 minutes as a radical generator. After thereaction was continued further for 30 minutes, unreacted maleicanhydride was removed while reducing the pressure in flask withaspirator. Next, this product was put in a glass-lined reactor, and,after 5 L of chloroform were added, gaseous chlorine was blown-in fromthe bottom of reactor under a pressure of 2 kg/cm², while irradiatingultraviolet rays to chlorinate. On the way, samplings were made andchloroform being solvent was distilled off by evaporator, respectively.Then, replacement was made with toluene/cyclohexane=70/30 (weight ratio)to obtain 20% by weight solutions of chlorinated propylenic randomcopolymer modified with maleic anhydride. Epicote 828 (from Yuka-ShellEpoxy Co., Ltd.) was added in amounts of 4% by weight based on resin asa stabilizer. The physical properties of the resins are shown inTable 1. The resin solutions obtained were allowed to stand for onemonth at room temperature, but no changes were seen in the liquid stateand appearance.

EXAMPLE-4

In a double shaft extruder with L/D=34 and φ=40 mm were put 500 g ofpropylenic random copolymer (propylene ca. 97%-ethylene ca. 3%) (fromNippon Polychem Co., Ltd., MFR=7.0 g/10 min, Tm=125° C.) produced byusing metallocene catalyst as a polymerization catalyst, 500 g of maleicanhydride and 15 g of dicumyl peroxide. The reaction was conductedmaking the retention time 10 minutes and barrel temperature 180° C.(first barrel through seventh barrel) and deaeration was made at theseventh barrel to remove unreacted maleic anhydride, thus obtainingmaleic anhydride-modified propylenic random copolymer. In a glass-linedreactor were put 500 g of this resin, and, after 5 L of chloroform wereadded, gaseous chlorine was blown-in from the bottom of reactor under apressure of 2 kg/cm², while irradiating ultraviolet rays to chlorinate.On the way, samplings were made and chloroform being solvent wasdistilled off by evaporator, respectively. Then, replacement was madewith toluene/cyclohexane=70/30 (weight ratio) to obtain 20% by weightsolutions of chlorinated propylenic random copolymer modified withmaleic anhydride. Epiol SB (from Nippon Oil and Fats Co., Ltd.) wasadded respectively in amounts of 4% based on resin as a stabilizer. Thephysical properties of the resins are shown in Table 1. The resinsolutions obtained were allowed to stand for one month at roomtemperature, but no changes were seen in the liquid state andappearance.

Comparative Example-1

An isotactic polypropylene (IPP) produced by using Ziegler-Nattacatalyst as a polymerization catalyst was fed into a double shaftextruder set at a barrel temperature of 350° C. to degrade thermally,thus obtaining an IPP with melt viscosity at 190° C. of about 2000mPa·s. Using 500 g of this resin, resin solutions of chlorinated IPPwith resin concentration of 20% by weight were obtained, similarly toExample 1. The physical properties of the resins are shown in Table 1.The resin solutions obtained were allowed to stand for one month at roomtemperature, but no changes were seen in the liquid state andappearance.

Comparative Example-2

Using 500 g of syndiotactic polypropylene (SPP, MFR=3.7 g/10 min), resinsolutions of chlorinated SPP with resin concentration of 20% by weightwere obtained, similarly to Example 1. The physical properties of theresins are shown in Table 1. The resin solutions obtained were allowedto stand for one month at room temperature, but no changes were seen inthe liquid state and appearance.

Comparative Example-3

An isotactic polypropylene (IPP) produced by using Ziegler-Nattacatalyst as a polymerization catalyst was fed into a double shaftextruder set at a barrel temperature of 350° C. to degrade thermally,thus obtaining an IPP with melt viscosity at 190° C. of about 2000mPa·s. Using 500 g of this resin, resin solutions of maleicanhydride-modified chlorinated IPP with resin concentration of 20% byweight were obtained, similarly to Example 2. The physical properties ofthe resins are shown in Table 1. The resin solutions obtained wereallowed to stand for one month at room temperature, but no changes wereseen in the liquid state and appearance.

Comparative Example-4

A syndiotactic polypropylene (SPP, MFR=3.7 g/10 min) was fed into adouble shaft extruder set at a barrel temperature of 350° C. to degradethermally, thus obtaining a SPP with melt viscosity at 190° C. of about2000 mPa·s. From 500 g of this resin, resin solutions of maleicanhydride-modified chlorinated SPP with resin concentration of 20% byweight were obtained, similarly to Example 2. The physical properties ofthe resins are shown in Table 1. The resin solutions obtained wereallowed to stand for one month at room temperature, but no changes wereseen in the liquid state and appearance.

Comparative Example-5

In Example 1, without adding a stabilizer, resin solutions ofchlorinated propylenic random copolymer with resin concentration of 20%by weight were obtained. When these resin solutions were allowed tostand for one month at room temperature, all of resin solutionsdiscolored into reddish brown.

[Measuring Method of Physical Properties of Resin]

MFR (Melt Flow Rate)

Measurement was made according to Melt Flow Rate in JIS-K-6758 TestingMethod of Polypropylene (conditions: 230° C., load 2.16 kgf).

Tm

The evaluation was made with both peak temperature of melting and endtemperature of melting at the time when sample (ca. 5 mg) was taken andmolten for 5 minutes at 200° C., and then, after lowering thetemperature to 40° C. at a rate of 10° C./min to crystallize, thetemperature was raised further to 200° C. at a rate of 10° C./min tomelt, using DSC measurement apparatus from Seiko Co.

Chlorine Content

Measurement was made according to JIS-K-7229.

Weight Average Molecular Weight (Mw) and Number Average Molecular Weight(Mn)

Measurement was made by means of GPC (standard substance: polystyreneresin). Moreover, in the table, Mw/Mn shows the molecular weightdistribution.

[Test of Liquid State]

The resin solution obtained was allowed to stand for one month at roomtemperature, and the liquid state and appearance were evaluatedvisually.

Criterion for Evaluation

-   ◯: No changes in the liquid state and appearance, even after one    month.-   Δ: Discoloration into reddish brown, after one month.-   x: Gelation, after one month.    [Primer Test]

After 100 g of each of resin solutions (solids 20%) obtained fromExamples 3 and 4 and Comparative examples 3 and 4 and 20 g of titaniumdioxide were kneaded for 3 hours in a sand mill, viscosity was adjustedwith xylene so as to give 13 to 15 seconds/20° C. through Ford cup No.4,and the mixture was painted onto an ultrahigh modulus PP plate (TX-933A,from Mitsubishi Chemical Industries Ltd.), poly(vinyl chloride) (PVC),polycarbonate (PC), PET, ABS or nylon-6 by air spray gun so as the filmthickness to become about 10 μm. Next, cure type two-component urethanepaint was painted (film thickness ca. 30 μm), which was dried for 30minutes at 80° C. and, after allowed to stand for 24 hours at roomtemperature, the physical properties were evaluated. The results ofprimer test are shown in Table 2.

Adherence

On the coated surface, 100 cross-cuts that reach the base were made atintervals of 1 mm, and cellophane adhesive tape was adhered closelythereon. Then, it was peeled off in the direction of 180° to judge withthe extent of remaining coated film.

Gasohol resistance: The painted plate was soaked into regulargasoline/ethanol=9/1 (v/v) for 120 minutes to observe the state ofcoated film.

-   Good: State of no abnormality in the coated film-   No good: State of abnormality in the coated film

Water resistance: The painted plate was soaked into warm water of 40° C.for 240 hours to examine the state of coated film and adherence.

-   Good: Case of entirely no peeling-   No good: Case of peeling caused    [Adhesiveness Test]

Heat Seal Test

Each of the resin solutions (solids 20 wt. %) obtained was coated ontoan untreated PP, poly (vinyl chloride) (PVC) or PET with coating rod#14. After dried for 24 hours at room temperature, coated surfaces weresuperposed and heat sealed under the press conditions of 2 sec, 80° C.and 1 kg/cm². After 24 hours, 180° peeling strength (g/cm) was measuredwith Tensilon (pulling speed: 50 mm/min). The results of adhesivenesstest are shown in Table 3.

[Ink Test]

After 100 g of each of resin solutions (solids 20 wt. %) obtained and 20g of titanium dioxide were milled for 3 hours in a sand mill, themixture was diluted with toluene so as the viscosity to become 25 to 30seconds/20° C. through #3 Zahn cup to prepare ink. With the inkobtained, adhesive tape peeling test and heat seal test were performed.The results of ink test are shown in Table 4.

Adhesive Tape Peeling Test

By the similar method to heat seal test, ink was coated onto anuntreated PP, poly(vinyl chloride) (PVC) or PET. After dried for 24hours at room temperature, cellophane adhesive tape was stuck ontoink-coated surface, and the state of coated surface when peeling off ata stroke was examined.

Criterion for Evaluation

-   Good: State of entirely no peeling-   No good: State of peeling caused

Heat Seal Test

Same as adhesiveness test. TABLE 1 Physical properties of resin and testof liquid state Maleic anhydride (wt. %) Test Chlorine (based on Averagemolecular of content chlorinated weight liquid (wt. %) resin) Mw MnMw/Mn state Ex. 1-1 20.5 — 49800 26200 1.90 ◯ Ex. 1-2 24.3 49700 260001.91 ◯ Ex. 1-3 32.0 49800 26200 1.90 ◯ Ex. 2-1 19.5 — 190000 104000 1.83◯ Ex. 2-2 25.0 191000 104000 1.83 ◯ Ex. 2-3 31.0 190000 103000 1.84 ◯Ex. 3-1 16.8 3.9 50800 27800 1.83 ◯ Ex. 3-2 19.5 3.5 52400 27600 1.90 ◯Ex. 3-3 26.1 3.3 53000 27400 1.93 ◯ Ex. 4-1 16.0 5.0 120000 62500 1.92 ◯Ex. 4-2 20.8 5.3 125000 64000 1.95 ◯ Ex. 4-3 25.1 5.1 123000 62400 1.97◯ Comp. 1-1 20.2 — — — — X Comp. 1-2 24.5 200000 68000 2.95 ◯ Comp. 1-331.5 210000 71000 2.94 ◯ Comp. 2-1 20.2 — 198000 101500 1.95 ◯ Comp. 2-230.5 198000 101000 1.96 ◯ Comp. 2-3 33.0 199000 101000 1.97 ◯ Comp. 3-115.2 3.8 — — — X Comp. 3-2 18.6 3.5 60000 27400 2.19 ◯ Comp. 3-3 26.03.4 60000 27400 2.19 ◯ Comp. 4-1 17.6 3.7 58000 29300 1.98 ◯ Comp. 4-222.6 3.4 58000 29100 1.99 ◯ Comp. 4-3 26.5 3.3 57800 29200 1.98 ◯ Comp.5-1 20.0 — 190000 104000 1.83 Δ Comp. 5-2 25.5 191000 104000 1.83 ΔComp. 5-3 31.5 190000 103000 1.84 ΔNote: With Comparative example 1-1 and Comparative example 3-1, themolecular weight could not be measured, since the resin solutionsimmediately after production were pudding-like.

TABLE 2 Results of primer test Prime material PP PVC PC PET ABS NylonAdherence Gasohol Water Adherence Adherence Adherence AdherenceAdherence (/100) resistance resistance (/100) (/100) (/100) (/100)(/100) Ex. 3-1 100 Good Good 100 100 100 100 100 3-2 100 Good Good 100100 100 100 100 3-3 100 Good Good 100 100 100 100 100 Ex. 4-1 100 GoodGood 100 100 100 100 100 4-2 100 Good Good 100 100 100 100 100 4-3 100Good Good 100 100 100 100 100 Comp. 3-1 — — — — — — — — 3-2 100 GoodGood 50 30 0 70 0 3-3 100 No good Good 30 10 0 50 0 Comp. 3-1 100 GoodGood 70 50 0 50 20 3-2 100 Good Good 60 0 0 50 20 3-3 100 Good Good 20 00 20 0Note: With Comparative example 3-1, each test could not be carried out,since the resin solution immediately after production was pudding-like.

TABLE 3 Results of adhesiveness test Heat seal strength (g/cm) PP primematerial PVC prime material PET prime material Ex. 1-1 860 830 830 -2780 770 750 -3 690 710 650 Ex. 2-1 900 820 780 -2 880 700 750 -3 730 680660 Ex. 3-1 1200 1050 1100 -2 1000 1000 1050 -3 850 920 900 Ex. 4-1 13001350 1400 -2 1100 1200 1380 -3 900 1140 1220 Comp. 1-1 — — — -2 500 30 0-3 400 0 0 Comp. 2-1 600 200 50 -2 500 100 30 -3 350 0 0 Comp. 3-1 — — —-2 700 50 0 -3 600 0 0 Comp. 4-1 1000 30 10 -2 800 10 0 -3 650 0 0 Comp.5-1 780 400 300 -2 680 200 280 -3 600 180 100Note:With Comparative example 1-1 and Comparative example 3-1, the testscould not be carried out, since the resin solutions immediately afterproduction were pudding-like.

TABLE 4 Results of ink test Peeling with adhesive tape Heat sealstrength (g/cm) PP prime PVC prime PET prime PP prime PVC prime PETprime material material material material material material Ex. 1-1 GoodGood Good 650 680 630 Ex. 1-2 Good Good Good 590 600 530 Ex. 1-3 GoodGood Good 450 460 420 Ex. 2-1 Good Good Good 700 720 750 Ex. 2-2 GoodGood Good 500 700 700 Ex. 2-3 Good Good Good 400 660 650 Ex. 3-1 GoodGood Good 900 1000 1050 Ex. 3-2 Good Good Good 850 940 980 Ex. 3-3 GoodGood Good 700 880 950 Ex. 4-1 Good Good Good 1000 1100 1200 Ex. 4-2 GoodGood Good 920 1050 1100 Ex. 4-3 Good Good Good 780 1000 1150 Comp. 1-1 —— — — — — Comp. 1-2 Good No good No good 400 0 0 Comp. 1-3 Good No goodNo good 320 0 0 Comp. 2-1 Good No good No good 580 100 30 Comp. 2-2 GoodNo good No good 410 40 0 Comp. 2-3 Good No good No good 290 0 0 Comp.3-1 — — — — — — Comp. 3-2 Good No good No good 530 0 0 Comp. 3-3 Good Nogood No good 440 0 0 Comp. 4-1 Good No good No good 680 0 0 Comp. 4-2Good No good No good 510 0 0 Comp. 4-3 Good No good No good 450 0 0Comp. 5-1 Good Good Good 540 200 200 Comp. 5-2 Good Good Good 480 50 250Comp. 5-3 No good No good No good 230 0 0Note: With Comparative example 1-1 and Comparative example 3-1, thetests could not be carried out, since the resin solutions immediatelyafter production were pudding-like.

Utilizability in the Industry

From Table 1, the chlorinated products of propylenic random copolymerproduced by using metallocene catalyst as a polymerization catalyst havegood liquid state, even if the chlorine content may be low. Moreover,from Table 2, the chlorinated products of propylenic random copolymerproduced by using metallocene catalyst as a polymerization catalyst havebetter gasohol resistance than that of the chlorinated products of IPPproduced by using conventional Ziegler•Natta catalyst as apolymerization catalyst. Furthermore, from Tables 2 through 4, thechlorinated products of propylenic random copolymer produced by usingmetallocene catalyst as a polymerization catalyst exhibit good adherencenot only onto polypropylene prime material, but also onto primematerials of poly(vinyl chloride), polycarbonate, PET, ABS, nylon, etc.It can be seen therefore that the binder resin compositions containingthese chlorinated propylenic random copolymers and/or carboxylgroup-containing chlorinated propylenic random copolymers are useful inthe industry and, in particular, effective for paint, adhesive, heatsealing agent, printing ink and primer.

1. A binder resin composition characterized by containing chlorinatedpropylenic random copolymer with weight average molecular weight of 3000to 250000, wherein propylenic random copolymer obtained bycopolymerizing propylene with other α-olefin in the coexistence ofmetallocene type catalyst is chlorinated to chlorine content of 10 to40% by weight, stabilizer and organic solvent.
 2. A binder resincomposition, wherein the chlorinated propylenic random copolymer ofclaim 1 is a carboxyl group-containing chlorinated propylenic randomcopolymer with weight average molecular weight of 30000 to 220000, graftpolymerized with α,β-unsaturated carboxylic acid or its anhydride inamounts of 0 to 20% by weight and then chlorinated to chlorine contentof 10 to 40% by weight, or chlorinated to chlorine content of 10 to 40%by weight and then graft polymerized with α,β-unsaturated carboxylicacid or its anhydride in amounts of 0 to 20% by weight.
 3. The binderresin composition of claim 1 or 2, wherein the propylenic randomcopolymer has a melting point (Tm) measured by differential scanningcalorimeter (DSC) of 115 to 165° C.
 4. A method of producing binderresin composition of claim 1 or 2, using the chlorinated propylenicrandom copolymer, wherein propylenic random copolymer with melting point(Tm) measured by differential scanning calorimeter (DSC) of 115 to 165°C. obtained by copolymerizing propylene with other α-olefin in thecoexistence of metallocene type catalyst is chlorinated to chlorinecontent of 10 to 40% by weight, after thermal degradation or withoutthermal degradation.
 5. A method of producing binder resin compositionof claim 4, wherein the chlorinated propylenic random copolymer is acarboxyl group-containing chlorinated propylenic random copolymer graftpolymerized with α,β-unsaturated carboxylic acid or its anhydride inamounts of 0 to 20% by weight and then chlorinated to chlorine contentof 10 to 40% by weight, or chlorinated to chlorine content of 10 to 40%by weight and then graft polymerized with α,β-unsaturated carboxylicacid or its anhydride in amounts of 0 to 20% by weight.
 6. A paintapplicable to films, sheets and moldings of polyolefin, poly(vinylchloride), polycarbonate, PET, ABS and nylon, having the binder resincomposition of any of claims 1 to 3 as an effective component.
 7. Aprinting ink applicable to films, sheets and moldings of polyolefin,poly(vinyl chloride), polycarbonate, PET, ABS and nylon, having thebinder resin composition of any of claims 1 to 3 as an effectivecomponent.
 8. An adhesive applicable to films, sheets and moldings ofpolyolefin, poly(vinyl chloride), polycarbonate, PET, ABS and nylon,having the binder resin composition of any of claims 1 to 3 as aneffective component.
 9. A heat sealing agent applicable to films, sheetsand moldings of polyolefin, poly(vinyl chloride), polycarbonate, PET,ABS and nylon, having the binder resin composition of any of claims 1 to3 as an effective component.
 10. A primer applicable to films, sheetsand moldings of polyolefin, poly (vinyl chloride), polycarbonate, PET,ABS and nylon, having the binder resin composition of any of claims 1 to3 as an effective component.